Stabilizer system for stabilizing pvc

ABSTRACT

Disclosed are stabilizer mixtures comprising at least a) one alkanolamine or one reaction product of a monofunctional or polyfunctional epoxide and ammonia or a monofunctional or polyfunctional dialkyl(aryl)amine or monoalkyl(aryl)amine, and b) one uracil or one initial product and an optional perchlorate salt

The invention relates to stabilizer mixtures, encompassing at least onealkanolamine, at least one uracil, and, if appropriate, one perchloratesalt, the mixtures being suitable for stabilizing chlorine-containingpolymers.

There are many additives which can stabilize PVC. Compounds of the heavymetals lead, barium and cadmium are particularly well suited to thispurpose, but are nowadays subject to criticism on environmental groundsor due to their heavy metal content (cf. “Plastics Additives Handbook”,H. Zweifel, Carl Hanser Verlag, 5th edn., 2001, pp. 427-483 and“Kunststoff Handbuch PVC” [Plastics Handbook PVC], volume 2/1, W.Becker/D. Braun, Carl Hanser Verlag, 2nd edn., 1985, pages 531-538; andalso Kirk-Othmer: “Encyclopedia of Chemical Technology”, 4th ed., 1994,Vol. 12, Heat Stabilizers, pp. 1071-1091).

Processors and consumers are increasingly refusing to use thesestabilizers.

Attempts therefore continue to find effective stabilizers and stabilizermixtures which are free from lead, barium and cadmium. The intentionhere is also to provide a composition which has stabilizing action withrespect to thermal and/or photochemical degradation and which, as aconstituent of halogen-containing polymers, gives excellent initialcolor and also gives color stability.

A mixing specification matched to the processing method can be providedhere, appropriate for the prevailing requirements, which may be based onhealth and safety at work, approval restrictions or process reliability.Surprisingly, this invention provides combinations of substances whichare physiologically non-hazardous in plastics and which in some casescertainly do not provide satisfactory processing stability when usedalone.

The applicant's specification WO 02/48249 A2 discloses compounds of theformula (I) in combination with at least one perchlorate salt. Thecomparative and inventive examples of this specification show thatcompounds of the general formula (I), used alone, do not contribute toacceptable initial color.

It has now been found that mixtures composed of a) at least onealkanolamine or one reaction product of a mono- or polyfunctionalepoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- ormonoalkyl(aryl)amine of the general formula (I), and of b) at least oneuracil of the general formula (II) or, respectively, of their precursorsof the general formula (III), and, if appropriate, one perchlorate salt,in particular a perchlorate of an alkali metal or of an alkaline earthmetal, are particularly suitable for stabilizing chlorine-containingpolymers, in particular PVC. The object set, to provide a stabilizermixture complying with the requirements placed upon initial color, hasbeen met via this novel combination. Further addition of a perchloratesalt, in particular a perchlorate of an alkali metal or of an alkalineearth metal, can improve the stabilization of chlorine-containingpolymers, in particular PVC.

The use of other classes of amines alone without perchlorate does notgive satisfactory processing stability, and in particular the initialcolor of the desired moldings does not differ substantially from that ofan unstabilized specimen, the consequence therefore being that therequirements for good initial color and process reliability desired byprocessors are not met.

The β-hydroxyalkanolamines used in combination with the uracils ofstructure (II) or with their precursors of structure (III) can assumethe function of improving initial color. This permits production ofmoldings with service properties complying with expectations over aprolonged period.

Surprisingly, synergistic action of the claimed combination, extendingbeyond the action of comparative mixing specifications comprising theindividual components, has also been found in systems with perchlorate.

The present invention therefore provides stabilizer mixtures,encompassing at least

-   -   a) one alkanolamine or/and one reaction product of a mono- or        polyfunctional epoxide and of ammonia or of a mono- or        polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the        formula (I) and    -   b) one uracil of the formula (II) or its precursor of the        formula (III), and, if appropriate,    -   c) one perchlorate salt.

For the alkanolamine of the formula (I) here

-   -   x=1, 2 or 3;    -   y=1, 2, 3, 4, 5 or 6;    -   n=from 1 to 10;    -   R¹ and R²=independently of one another H, C₁-C₂₂-alkyl, —[—(CHR³        _(a))_(y)—CHR³ _(b)—O—]_(n)—H, —[—(CHR³ _(a))_(y)—CHR³        _(b)—O—]_(n)—CO—R⁴, C₂-C₂₀-alkenyl, C₂-C₁₈-acyl,        C₄-C₈-cycloalkyl, where this may have OH substitution in the        β-position, C₆-C₁₀-aryl, C₇-C₁₀-alkaryl or C₇-C₁₀-aralkyl, or,        if x=1, R¹ and R² may also, together with the N, form a closed        ring having from 4 to 10 members, composed of carbon atoms and,        where appropriate, of up to 2 heteroatoms, or if x=2, R¹ may        also be C₂-C₁₈-alkylene which, at both β-carbon atoms, may have        OH substitution and/or have interruption by one or more O atoms        and/or by one or more NR² groups, or be dihydroxy-substituted        tetrahydrodicyclopentadienylene, dihydroxy-substituted        ethylcyclohexanylene, dihydroxy-substituted 4,4′-(bisphenol A        dipropyl ether)ylene, isophoronylene, dimethylcyclohexanylene,        dicyclohexylmethanylene or 3,3′-dimethyldicyclohexylmethanylene,        and if x=3, R¹ may also be trihydroxy-substituted (tri-N-propyl        isocyanurate)triyl;    -   R³a and R³ _(b)=independently of one another C₁-C₂₂-alkyl,        C₂-C₆-alkenyl, C₆-C₁₀-aryl, H or CH₂—X—R⁵, where X═O, S, —O—CO—        or —CO—O—;    -   R⁴=C₁-C₁₈-alkyl/alkenyl or phenyl; and    -   R⁵=H, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl or C₆-C₁₀-aryl.

The invention also provides stabilizer mixtures where the alkanolamineis a reaction product of a mono- or polyfunctional epoxide and ofammonia or of a mono- or polyfunctional dialkyl(aryl)- ormonoalkyl(aryl)amine.

Examples of the alkanolamines of the general formula (I) are compoundswhere R¹ and R²=methyl, ethyl, propyl, butyl, cyclohexyl, octyl, lauryl,tetradecyl, hexadecyl, stearyl, oleyl, allyl, phenyl or benzyl orhydroxyalkyl and R═H, methyl, ethyl, propyl or butyl. Preference isgiven to alkanolamines where R¹=lauryl, tetradecyl, hexadecyl, stearyl,or oleyl, where R²=hydroxyalkyl. It is also possible to use ethoxylatesand propoxylates of triethanol- and tri-isopropanolamine, and also offatty amines of vegetable or animal origin. Preference is given totrialkanolamines and monoalkyl/alkenyldialkanolamines where R³═H ormethyl and y=1, in particular fatty amines which have been reacted twicewith ethylene oxide or with propylene oxide. Other compounds with verygood suitability can be found in the following list.

Methyl- or dimethylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Propyl- or dipropylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Isopropyl- or diisopropylamine reacted once or twice with ethylene oxideor with propylene oxide.

Butyl- or dibutylamine reacted once or twice with ethylene oxide or withpropylene oxide.

Isobutyl- or diisobutylamine reacted once or twice with ethylene oxideor with propylene oxide.

Pentyl- or dipentylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Isopentyl- or diisopentylamine reacted once or twice with ethylene oxideor with propylene oxide.

Hexyl- or dihexylamine reacted once or twice with ethylene oxide or withpropylene oxide.

Isohexyl- or diisohexylamine reacted once or twice with ethylene oxideor with propylene oxide.

Heptyl- or diheptylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Isoheptyl- or diisoheptylamine reacted once or twice with ethylene oxideor with propylene oxide.

Octyl- or dioctylamine reacted once or twice with ethylene oxide or withpropylene oxide.

Isooctyl- or diisooctylamine reacted once or twice with ethylene oxideor with propylene oxide.

Nonyl- or dinonylamine reacted once or twice with ethylene oxide or withpropylene oxide.

Isononyl- or diisononylamine reacted once or twice with ethylene oxideor with propylene oxide.

Decyl- or didecylamine reacted once or twice with ethylene oxide or withpropylene oxide.

Isodecyl- or diisodecylamine reacted once or twice with ethylene oxideor with propylene oxide.

Undecyl- or diundecylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Isoundecyl- or diisoundecylamine reacted once or twice with ethyleneoxide or with propylene oxide.

Dodecyl- or didodecylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Isododecyl- or dii-sododecylaamine react-ed once or twice with ethyleneoxide or with propylene oxide.

Tridecyl- or ditridecylamine reacted once or twice with ethylene oxideor with propylene oxide.

Isotridecyl- or diisotridecylamine reacted once or twice with ethyleneoxide or with propylene oxide.

Tetradecyl- or ditetradecylamine reacted once or twice with ethyleneoxide or with propylene oxide.

Hexadecyl- or dihexadecylamine reacted once or twice with ethylene oxideor with propylene oxide.

Octadecyl- or dioctadecylamine reacted once or twice with ethylene oxideor with propylene oxide.

Eicosyl- or dieicosylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Docosyl- or didocosylamine reacted once or twice with ethylene oxide orwith propylene oxide.

N-Methylbutylamine reacted with ethylene oxide or with propylene oxide.

N-Ethylbutylamine reacted with ethylene oxide or with propylene oxide.

Allyl- or diallylamine reacted once or twice with ethylene oxide or withpropylene oxide.

Crotyl- or dicrotylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Octadecenyl- or dioctadecenylamine reacted once or twice with ethyleneoxide or with propylene oxide.

Benzyl- or dibenzylamine reacted once or twice with ethylene oxide orwith propylene oxide.

Cyclohexyl- or dicyclohexylamine reacted once or twice with ethyleneoxide or with propylene oxide.

N-Methylcyclohexylamine reacted with ethylene oxide or with propyleneoxide.

N-Ethylcyclohexylamine reacted with ethylene oxide or with propyleneoxide.

4-Vinyl-l-cyclohexene diepoxide reacted twice with diethanol- ordiisopropanolamine.

Dicyclopentadiene diepoxide reacted twice with diethanol- ordiisopropanolamine.

Bisphenol A diglycidyl ether reacted twice with diethanol- ordiisopropanolamine.

Trisglycidyl isocyanurate reacted three times with diethanol- ordiisopropanolamine.

Preference is given to trialkanolamines andmonoalkyl/alkenyldialkanolamines where R³ _(a) and R³ _(b)=independentlyof one another H or methyl and y=1.

The compounds of the general formula (I) where y=from 1 to 6, i.e.having up to 6 methylene groups between the amino group and thehydroxy-substituted carbon atom, have been found to be suitable for useas a PVC stabilizer in combination with a perchlorate salt.

According to the invention it is also possible to use compounds of thegeneral formula (I) where x=2, i.e. compounds which have twohydroxyalkylamino groups per molecule. Examples of these areN,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine,N,N,N′,N′-tetrakis(2-hydroxy-1-propyl)ethylenediamine,N,N,N′,N′-tetrakis(2-hydroxyethyl)propylenediamine andN,N,N′,N′-tetrakis(2-hydroxy-1-propyl)-1propylenediamine andN,N,N′,N′-tetrakis(2-hydroxyethyl)hexamethylenediamine, preference beinggiven to four-fold reactions of 1,6-hexamethylene- or1,8-octamethylenediamine or neopentanediamine with ethylene oxide orwith propylene oxide, or analogous reactions ofbisaminomethylcyclohexane or isophoronediamine or4,4′-diaminodicyclohexylmethane or3,3′-dimethyl-4,4′-diaminodicyclohexylmethane.

According to the invention, it is also possible to use compounds of thegeneral formula (I) where x=3, i.e. those which have threehydroxyalkylamino groups per molecule. An example of these is a reactionproduct of trisglycidyl isocyanurate with mono- or diethanolamine ormono- or dipropanolamine.

The alkanolamines of the general formula (I) are chemicals which can bepurchased or can be prepared by known methods via N-alkylation of anappropriate amine or ammonia (cf. Kirk-Othmer, Vol. 2, Alkanolamines).

Examples of the preferred alkanolamines of the general formula (I) aretris(2-hydroxyethyl)amine, tris(2-hydroxy-1-propyl)amine,bis(2-hydroxyethyl)-2-hydroxy-1-propylamine,N-n-butyl-N,N-bis(2-hydroxy-ethyl)amine, N,N-bis(n-butyl)-N-(2-hydroxyethyl)amine,N-(3-n-butyloxy-2-hydroxy-1-propyl)-N,N-bis(2-hydroxyethyl)amine,N-(1,3-dihydroxy-2-hydroxymethyl-2-propyl)-N,N-bis(2-hydroxyethyl)amine,N,N-bis-(2-hydroxyethyl)-N-palmitylamine,N,N-bis(2-hydroxy-ethyl)-N-oleylamine,N,N-bis(2-hydroxyethyl)-N-stearylamine,N,N-bis(2-hydroxyethyl)-N-stearylamine, N-(2-hydroxyethyl)morpholine andN-(2,3-dihydroxy-1-propyl)morpholine, bishydroxyethylpiperazine andbishydroxyisopropylpiperazine and reaction products of glycidyl etherswith mono- or dialkylamine or ammonia, and also the alkanolaminesderived therefrom, for example ethanolamine, diethanolamine,n-propanolamine, isopropanolamihne, n-dipropanolamine, orisodipropanolamine.

Very particular preference is given to adducts of olefin oxides, such asoctene oxide, decene oxide, dodecene oxide, tetradecene oxide,hexadecene oxide, octadecene oxide, eicosene oxide and docosene oxide,and also epoxystearyl alcohol with diethanol- or diisopropanolamine.These compounds with an OH function in the β-position at both ends of arelatively long alkyl chain, for exampleN-(2-hydroxyhexadecyl)diethanolamine, N-(2-hydroxy-3-octyloxypropyl)diethanolamine, N-(2-hydroxy-3-decyloxypropyl)diethanolamine,N-(2-hydroxy-3-octyloxypropyl)diethanolamine andbis-N-(2-hydroxy-3-phenyloxypropyl)ethanolamine are a particularlysuitable component in the stabilizer systems of the invention.

This list is given only by way of example and does not claim to becomprehensive.

The amounts to be used of the compounds of the formula (I) to achievestabilization in chlorine-containing polymer are advantageously from0.01 to 10% by weight, preferably from 0.05 to 5% by weight, inparticular from 0.1 to 3% by weight.

The inventive composition comprises, alongside at least onerepresentative of the alkanolamines of the structure (I), at least onerepresentative of the uracils of the general structure (II). Accordingto the invention, the group of the uracils is defined as that of thederivatives of structure (II) and also that of the cyanoacetylureas ofthe structure (III), which are precursors of the uracils.

Compounds of the formula (II) have previously been described in DE-A-1694 873, EP-A-0 065 934, EP-A-0 041 479, and EP-A-0 768 336, and can beprepared by known methods in a process involving one or more steps.

where

-   -   R1 and R2, independently of one another, are C1-C24-alkyl, which        may have interruption by —CO₂— and/or by 1 or more oxygen atoms,        and/or may have substitution by one or more OH groups, examples        here being —CH₂—O—CH₂—CH₂—O—CH₃, —CH₂—O—CH₂—CH₂—CH₂—O—CH₃,        —CH₂—O—CH₂—CH₂—CH₂—CH₂—O—CH₃, —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₃,        —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₃, etc. or are        C3-C24-alkenyl, branched or unbranched, or are C5-C8-cycloalkyl,        unsubstituted or substituted with from 1 to 3 C1-C4-alkyl,        C1-C4-alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy        groups, or with Cl atoms, or are C7-C9-phenylalkyl,        unsubstituted or substituted on the phenyl ring with from 1 to 3        C1-C4-alkyl, C1-C4-alkoxy, or C5-C8-cycloalkyl groups, or with        hydroxy groups, or with Cl atoms, and R1 or R2 may also be        hydrogen, and Y is S or O. For compounds of the formula (II)        here:

examples of C1-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl or tert-butyl. Preference is given to C1-C4-alkyl,if appropriate with interruption by —CO_(2—.)

Examples of C1-C24-alkyl other than the radicals just mentioned arepentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, nonyl,undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl ortetracosyl.

Examples of the alkenyl radicals are vinyl, allyl, methallyl, 1-butenylor 1-hexenyl, 1-octenyl, 2-octenyl, decenyl, undecenyl, tetradecenyl,hexadecenyl, octadecenyl and eicosenyl, preferably allyl. The alkyl oralkenyl radicals may be branched or unbranched radicals.

Examples of C1-C4-alkoxy are methoxy, ethoxy, propoxy, isopropoxy,butoxy or isobutoxy.

Examples of C5-C8-cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl orcyclooctyl.

Examples of C7-C9-phenylalkyl are benzyl, 1- or 2-phenylethyl,3-phenylpropyl, α,α-dimethylbenzyl or 2-phenylisopropyl, preferablybenzyl.

If the cycloalkyl groups or the phenyl group of the phenylalkyl radicalshave substitution, preference is then given to two or one substituent(s), particular preference among the substituents being given tochlorine, hydroxy, methyl or methoxy.

Examples of C3-C6-alkenyl are vinyl, allyl, methallyl, 1-butenyl or1-hexenyl, preferably allyl.

If the alkyl radicals have interruption, they necessarily include atleast 2 carbon atoms. —CO₂— here means a

group.

Examples of C1-C22-alkyl radicals with interruption by —CO2— arebranched or straight-chain radicals, e.g. methoxycarbonylmethyl,methoxycarbonylethyl, methoxycarbonylpropyl, methoxycarbonylbutyl,methoxycarbonylhexyl, methoxycarbonyloctyl, ethoxycarbonylmethyl,ethoxycarbonylethyl, ethoxycarbonylpropyl, ethoxycarbonylbutyl,ethoxycarbonylhexyl, ethoxycarbonyloctyl, n-propoxycarbonylmethyl,n-propoxycarbonylethyl, n-propoxycarbonylbutyl, n-propoxycarbonylhexyl,n-propoxycarbonyloctyl, isopropoxycarbonylmethyl,isopropoxycarbonylethyl, isopropoxycarbonylbutyl,isopropoxycarbonylhexyl, isopropoxycarbonyloctyl,n-butoxycarbonylmethyl, n-butoxycarbonylethyl, n-butoxycarbonvlbutyl,n-butoxycarbonyl-hexyl or tert-butoxycarbonylmethyl. This list makes noclaim to be comprehensive, but gives the structural principle, which isreadily comprehensible to the person skilled in the art.

By way of example, methoxycarbonylethyl is preferred.

Preference is given here to compounds of the formula (II), where R1 andR2, independently of one another, are C1-C18-alkyl and hydrogen.

It is particularly preferable either that R1 and R2 are identical andare methyl, ethyl, propyl, butyl, allyl or octyl, or that they aredifferent and are ethyl and allyl.

If only one of the two substituents R1 or R2 is. hydrogen, the carbonchain of the remaining radical is larger than C2, and the above thenapplies correspondingly to the possible further substitution pattern. R1or R2 can therefore be C3-C24-alkyl., which may have interruption by—CO₂— and/or by 1 or more oxygen atoms, and/or may have substitution byone or more OH groups, or can be C3-C24-alkenyl, branched or unbranched,or can be C5-C8-cycloalkyl, unsubstituted or substituted with from 1 to3 C1-C4-alkyl, C1-C4-alkoxy, or C5-C8-cycloalkyl groups, or with hydroxygroups, or with Cl atoms, or can be C7-C9-phenylalkyl, unsubstituted orsubstituted on the phenyl ring with from 1 to 3 C1-C4-alkyl,C1-C4-alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy groups, orwith Cl atoms. Preference is given to the monosubstituted, in the 1- or3-position of the formula (II), alkyl, alkenyl or alkoxyalkylderivatives where R1 or R2 is propyl or butyl or cyclohexyl or isC3-C6-alkyl interrupted by an oxygen atom. Examples of particularlypreferred compounds are: 1-propyl-2-aminouracil, 1-propyl-4-aminouracil,1-allyl-2-aminouracil, 1-allyl-4-aminouracil,1-methoxyethyl-2-aminouracil, 1-methoxyethyl-4-aminouracil.

According to the invention, it is also possible to use thecyanoacetylureas (III), which are the synthetic precursors of theuracils, in combination with the structures of the formula (I). Theseare known to the person skilled in the art and are described in U.S.Pat. No, 2,598,936, and in the applicant's specification U.S. Pat. No,6,211,270, and in J. Org. Chem. 16, 1897-1890 (1951), and can beprepared by known methods. The starting ureas are commercially availableor can be prepared by known processes.

Cyanoacetylureas of the formula (III)

where

-   -   Y is oxygen or sulfur, and    -   R1 is C1-C24-alkyl, which may have interruption by —CO2— and/or        by oxygen atoms, and/or may have substitution by from 1 to 3 OH        groups, or is C3-C24-alkenyl, C7-C10-phenylalkyl,        C5-C8-cycloalkyl, C7-C10-alkylphenyl, phenyl or naphthyl, where        in each case the aromatic radical may have substitution by —OH,        C1-C12-alkyl and/or OC1-C4-alkyl, and R2 is as defined for R1,        or, if R1 is hydrogen then R2 can also be C3-C24-alkyl, which        may have interruption by —CO2— and/or by oxygen atoms and/or may        have substitution by from 1 to 3 OH groups, or can be        C3-C24-alkenyl, C7-C10-phenylalkyl, C5-C8-cycloalkyl,        C7-C10-alkylphenyl, phenyl or naphthyl, where in each case the        aromatic radical may have substitution by -OH, by C1-C12-alkyl        and/or by OC1-C4-alkyl, have particularly good suitability in        the combination described according to the invention for        stabilizing chlorine-containing polymers, e.g. PVC.

For compounds of the formula (III):

Examples of C1-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl or tert-butyl. Examples of C₁-C24-alkyl, other thanthe radicals just mentioned, are pentyl, hexyl, heptyl, octyl,2-ethylhexyl, isooctyl, decyl, nonyl, undecyl or dodecyl, and alsotetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl.Preference is given to C₁-C8-alkyl, if appropriate having interruptionby —CO2—. Examples of C5-C8-cycloalkyl are cyclopentyl, cyclohexyl,cycloheptyl or cyclooctyl, preferably cyclohexyl. Examples ofC7-C10-alkylphenyl are tolyl or mesityl, in particular tolyl. Examplesof C7-C10-phenylalkyl are benzyl, 1- or 2-phenylethyl, 3-phenylpropyl,α,α-dimethylbenzyl or 2-phenylisopropyl, preferably benzyl and2-phenethyl, in particular benzyl.

If the aromatic radical has substitution, it preferably has three, twoor in particular one substituent, and the substituents are in particularhydroxy, methyl, ethyl, methoxy or ethoxy.

Examples of C3-C8-alkenyl are allyl, methallyl, 1-butenyl, 1-hexenyl,1-octenyl or 2-octenyl, preferably allyl.

If the alkyl radicals have interruption, they necessarily include atleast 2 carbon atoms.

—CO₂— here is a

group.

Examples of alkyl radicals with interruption by —CO₂— can be found inthe text associated with formula (II). Preference is given here tocompounds of the formula (III) where

Y is oxygen, and also to those where the radicals R1 and R2 areidentical. Other advantageous compounds are those where Y is sulfur.

Further preference is given to compounds of the formula (III) where R1and R2 are C1-C8-alkyl, C3-C5-alkenyl, benzyl or 2-phenethyl.

Particular preference is given to compounds of the formula (III) whereR1 and R2 are C₁-C4-alkyl, allyl or benzyl.

Examples which may be mentioned are N,N′-dimethyl-N-cyanoacetylurea,N,N′-diethyl-N-cyanoacetylurea, N,N′-dioctyl-N-cyanoacetylurea, etc.This list is given only by way of example and does not make any claim tobe comprehensive.

Other preferred compounds here are those of the formula (III) where

Y is oxygen, and also those where the radicals R1 and R2 differ from oneanother. In particular for RI=H. R2 is then C3-C12-alkyl which may haveinterruption by —CO₂— and/or by oxygen atoms, and/or may havesubstitution by from 1 to 3 OH groups, or is then C3-C12-alkenyl,C7-C10-phenylalkyl, C5-C8-cycloalkyl, C7-C10-alkylphenyl, phenyl ornaphthyl, where in each case the aromatic radical may have substitutionby -OH, by C1-C12-alkyl and/or by OC₁-C4-alkyl. Other advantageouscompounds are those where Y is sulfur. Particular preference is given tocompounds of the formula (III) where R1═H and

R2=C3-C8-alkyl, methoxyethyl, allyl or benzyl.

It should expressly be mentioned here that the reaction of thecyanoacetylureas of the general formula (III) to give the correspondinguracils of the general formula (II) can take place even beforepreparation of the stabilizer has ended. This is known to the personskilled in the art from the literature and derives from the syntheticprinciple of preparation of uracils from cyanoacetylureas. By way ofexample, N,N′-dibutyl-N-cyanoacetylurea (formula (III): R1=R2 =butyl)will react to give the analogous 1,3-dibutyl-4-aminouracil. Particularlyif the matrix here comprises basic compounds. This precondition ismoreover met merely by the other possible components of the matrix, e.g.commercially available calcium stearate or zeolite. In this context, thematrix in the selected inventive examples comprises the alkanolaminealone, or one or more compounds from the group of the plastics additivesand plastics stabilizers and of the halogen-containing organic plastics.If the matrix comprises liquid constituents, this reaction isaccelerated in accordance with the kinetics of chemical reactions.

Representatives of the general formula (I) which are liquid at roomtemperature or at processing temperature are particularly suitable forthis purpose.

This reaction of the cyanoacetylurea to give the uracil is in particularalso promoted by temperature increases brought about via mixing orprocessing, or brought about via the preparation of the stabilizer, andthese may be spray processes or melting processes. It is not necessaryfor the reaction here to proceed to completion. The two species may bepresent alongside one another in various ratios. However, certainconditions can give practically quantitative conversion. There are norestrictions per se on the selection of the basic compounds for thereaction of the cyanoacetylurea intermediate to give the uracil.Suitable compounds are any of those whose aqueous or alcoholic extractreacts as a base, or which in any other way induce the reaction,examples being:

alkali metal hydroxides, alkaline earth metal hydroxides, zeolites,Alcamizer products or amines. The reaction may take place before the endof the process to prepare the stabilizer, or during the process ofmixing the stabilizer components alone, or in the presence of the entireformulation, either in the mixer or in the subsequent course ofprocessing.

The amount of the compounds of the formula (III) to be used to achievestabilization in the chlorine-containing polymer is advantageously from0.01 to 10% by weight, preferably from 0.05 to 5% by weight, inparticular from 0.1 to 3% by weight.

The invention also provides combinations of the stabilizer mixturesencompassing at least alkanolamine or a reaction product of a mono- orpolyfunctional epoxide and of ammonia or of a mono- or polyfunctionaldialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I) and uracils ofthe formula (II) or their precursors of the formula (III) encompassingat least one halogen-containing oxyacid, e.g. a perchlorate salt.

The perchlorate salts are known to the person skilled in the art,examples are those of the formula M(ClO₄)n, where M is Li, Na, K, Mg,Ca, Sr, Ba, Zn, Al, La, Ce, or a hydrotalcite layer-lattice cation, oran organic onium salt cation. The index n is 1, 2 or 3, as appropriatefor the valency of M, or if a hydrotalcite layer-lattice cation ispresent 0<n<1.

These perchlorate salts may be used in various familiar supply forms;e.g. in the form of a salt or solution in water or in an organicsolvent, as they stand, or absorbed onto a carrier material such as PVC,Ca silicate, zeolites or hydrotalcites. Examples are perchlorate saltsdissolved or complexed using alcohols (polyols, cyclodextrins) or usingether alcohols or ester alcohols or crown ethers or plasticizers.Partial esters of the polyols are to be regarded as ester alcohols here.In the case of polyhydric alcohols or polyols it is also possible to usetheir dimers, trimers, oligomers and polymers, examples being di-, tri-,tetra- and polyglycols, and also di-, tri- and tetrapentaerythritol orpolyvinyl alcohol in various degrees of polymerization. Other solventswhich may be used are phosphate esters, and also cyclic and acycliccarbonic esters. Other embodiments are described in EP 0 394 547, EP 0457 471 and WO 94/24200. Depending on the carrier material used orprocess for application to the carrier, the structure of the perchloratesalts may be either amorphous or else semicrystalline or crystalline.The person skilled in the art is also aware of mixtures of the variousstates of aggregation.

It is preferable to use sodium/potassium perchlorate salts.

Examples of the amount of the perchlorates that can be used are from0.001 to 5 parts by weight, advantageously from 0.01 to 3 parts byweight, particularly preferably from 0.01 to 2 parts by weight, based on100 parts by weight of PVC.

The use of ethanolammonium perchlorate salts for inhibitingdiscoloration of chlorine-containing resin is disclosed in JP-A 61-9451.These are perchlorate salts with ammonium-salt structure, which can beobtained via addition of primary, secondary or tertiary ethanolamines toa perchloric acid solution. Ammonium perchlorate salts are generallycompounds sensitive to heat and shock and therefore create a certainrisk of explosion, making them unsuitable for industrial applications.

The invention also provides combinations of the stabilizer mixturescomposed of at least one alkanolamine or of a reaction product of amono- or polyfunctional epoxide and of ammonia or of a mono- orpolyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I)and of uracils of the formula (II) or of their precursors of the formula(III) with at least one other conventional additive or conventionalstabilizer.

The invention also provides combinations of the stabilizer mixturescomposed of at least one alkanolamine or one reaction product of a mono-or polyfunctional epoxide and of ammonia or of a mono- or polyfunctionaldialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I) and of uracilsof the formula (II) or of their precursors of the formula (III) with atleast one perchlorate salt and with at least one other conventionaladditive or conventional stabilizer.

The inventive compositions may therefore also have been treated withother conventional additives, such as polyols and disaccharide alcohols,hydroxycarboxylic acids or their salts, glycidyl compounds,hydrotalcites, zeolites (aluminosilicates of alkali metals or alkalineearth metals), compounds from the group of the calcium aluminumhydroxides or their hydrates, compounds from the group of the calciumaluminum hydroxohydrogenphosphites or their hydrates, compounds from thegroup of the aluminum hydroxides or their hydrates, compounds from thegroup of the calcium aluminum hydroxo(hydrogen)carbonates or theirhydrates, compounds from the group of the lithium layer-latticecompounds or their hydrates, fillers, metal soaps, alkali metalcompounds and alkaline earth metal compounds, fillers/pigments,lubricants, plasticizers, phosphites, pigments, epoxidized fatty acidesters and other epoxy compounds, flame retardants, antioxidants, UVabsorbers, gelling agents, compatibilizers, antistatic agents,antifogging agents, light stabilizers, optical brighteners and blowingagents. Particular preference is given to epoxidized soy oils, alkalineearth metal soaps or aluminum soaps and phosphites.

Examples of these additional components are listed and explained at alater stage below (cf. “Handbook of PVC Formulating” by E. J. Wickson,John Wiley & Sons, New York 1993).

Stabilization of chlorine-containing polymers, in particular PVC, bymeans of hydrocalumites, catoites and calcium aluminumhydroxohydrogenphosphites is disclosed in WO 92/13914, WO 93/25613, DE 3941 902 and DE 4 106 411. The compounds from the group of the calciumaluminum hydroxides or their hydrates are generally described in“Ullmann's Encyclopedia of Industrial Chemistry” (5th edition, 1986):Vol. A5—Cement and Concrete (pp. 505 et seq.); Kirk-Othmer “Encyclopediaof Chemical Technology” (4th edition, 1993): Vol. 5—Cement (pp. 572 etseq.); P. Barnes “Structure and Performance of Cements” (Appl. Sci.Publ. N. Y., 1983); F. M. Lea “The Chemistry of Cement and Concrete” (E.Arnold Publ. London, 1971); H. F. W. Taylor “Cement Chemistry” (Acad.Press, London, 1992)—chapter 6: Hydrated aluminate phases (pp. 167 etseq.).

The stabilizing action of lithium layer-lattice compounds on the PVC isdescribed by way of example in EP-A-0 761 756 and in DE-A-4 425 275. Allof these compounds may have been surface-modified, if desired.

Polyols and Disaccharide Alcohols

Examples of compounds of this type which may be used are:pentaerythritol, dipentaerythritol, tripentaerythritol,trimethylolethane, bistrimethylolpropane, inositol (cyclitols),polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol(hexitols), maltitol, isomaltitol, cellobiitol, lactitol, Lycasin,mannitol, lactose, leucrose, tris(hydroxyethyl) isocyanurate,tris(hydroxypropyl) isocyanurate, Palatinitol,tetramethylolcyclohexanol, tetramethylolcyclopentanol,tetramethylolcyclopyranol, xylitol, arabinitol (pentitols), tetritols,glycerol, diglycerol, polyglycerol, thiodiglycerol or1-0-α-D-glycopyranosyl-D-mannitol dihydrate. Among these, preference isgiven to the disaccharide alcohols. It is also possible to use polyolsyrups, such as sorbitol syrup, mannitol syrup and maltitol syrup.

Examples of the amount which may be used of the polyols are from 0.01 to20 parts by weight, advantageously from 0.1 to 20 parts by weight and inparticular from 0.1 to 10 parts by weight, based on 100 parts by weightof PVC.

Hydroxycarboxylic Acids

Use may be made of salts or mixtures of salts of hydroxycarboxylic acidshaving fewer than 4 hydroxy groups and fewer than 10 carbon atoms. Amongthese are compounds listed in detail in the patent application WO02/06389. Compounds having one or two hydroxy groups have provenparticularly effective. Other substitution patterns may be present,examples being aldehyde, keto, acyl, amino, aminoalkyl, aminoaryl and/orhalide substituents. If the compound bears two or more acid functions,at least one of these is in salt form. The salts are preferably thoseselected from the group Li, K, Na, Ca, Mg, Ba, Sr, Al, Fe, La, Ce, Mn orzinc. Preference, depending on the application, is particularly given tothe salts of lactic acid, e.g. sodium lactate, or salts of citric acid.

Glycidyl Compounds

They contain the glycidyl group

bonded directly to carbon, to oxygen atoms, to nitrogen atoms or tosulfur atoms, where either R₁ and R₃ are both hydrogen, R₂ is hydrogenor methyl and n=0 or R₁ and R₃ together are —CH₂—CH₂— or —CH₂—CH₂—CH₂—,R₂ is then hydrogen and n=0 or 1.

It is preferable to use glycidyl compounds having two functional groups.However, it is also possible in principle to use glycidyl compoundshaving one, three or more functional groups.

Diglycidyl compounds having aromatic groups are mainly used. The amountpreferably used of the terminal epoxy compounds is at least 0.1 part,for example from 0.1 to 50 parts by weight, advantageously from 1 to 30parts by weight and in particular from 1 to 25 parts by weight, based on100 parts by weight of PVC.

Hydrotalcites

The chemical composition of these compounds is known to the personskilled in the art, e.g. from the patents DE 3 843 581, U.S. Pat. No.4,000,100, EP 0 062 813 and WO 93/20135.

Compounds from the hydrotalcite series may be described by the followinggeneral formulaM²⁺ _(1-x)M³⁺ _(x)(OH)₂(A^(b−))_(x/b).d H₂O,where

M²⁺=one or more of the metals selected from the group consisting of Mg,Ca, Sr, Zn and Sn

M³⁺=Al or B,

A^(n) is an anion of valency n, b is a number from 1 to 2,

0<x0.5,

m is a number from 0 to 20.

Preference is given to compounds with

A^(n)=OH⁻, ClO₄ ⁻, HCO₃ ⁻, CH₃COO⁻, C₆H₅COO⁻, CO₃ ²³¹ , (CHOHCOO)₂ ²⁻,(CH₂COO)₂ ²⁻, CH₃CHOHCOO⁻, HPO₃ ⁻ or HPO₄ ²⁻.

Examples of hydrotalcites are Al₂O₃.6MgO.CO₂.12H₂O (i), Mg₄.5Al₂(OH)₁₃.CO₃.3.5H₂O (ii), 4MgO.Al₂O₃.CO₂.9H₂O (iii), 4MgO.Al₂O₃.CO₂.6H₂O,ZnO.3MgO.Al₂O₃.CO₂.8-9H₂O and ZnO.3MgO. AlO₃. CO₂.5-6H₂O. Types i, iiand iii are very particularly preferred.

Zeolites (Aluminosilicates of Alkali Metals and/or of Alkaline EarthMetals)

These may be described by the following general formulaM_(x/n)[(AlO₂)_(x)(SiO₂)_(y)].wH₂O, where n is the charge on the cationM;

M is an element of the first or second main group, such as Li, Na, K,Mg, Ca, Sr or Ba;

y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and

w is a number from 0 to 300, preferably from 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulae

Na₁₂Al₁₂Si₁₂O₄₈.27 H₂O [zeolite A], Na₆Al₆Si₆O₂₄.2NaX.7.5H₂O, X═OH,halogen, ClO₄ [sodalite]; Na₆Al₆Si₃₀O₇₂. 24 H₂O; Na₈Al₈Si₄₀O₉₆.24 H₂O;Na₁₆Al₁₆Si₂₄O₈₀.16 H₂O; Na₁₆Al₁₆Si₃₂O₉₆.16 H₂O; Na₅₆Al₅₆Si₁₃₆O₃₈₄.250H₂O [zeolite Y], Na₈₆Al₈₆Si₁₀₆O₃₈₄.264 H₂O zeolite X];

or the zeolites which can be prepared by partial or complete exchange ofthe Na atoms by Li atoms, K atoms, Mg atoms, Ca atoms, Sr atoms or Znatoms, for example (Na, K)₁₀Al₁₀Si₂₂O₆₄.20 H₂O;Ca_(4.5)Na₃[(AlO₂)₁₂(SiO₂)₁₂]. 30 H₂O; K₉Na₃[(AlO₂)₁₂(SiO₂)₁₂].27 H₂O.

Very particular preference is given to Na zeolite A and Na zeolite P.

The hydrotalcites and/or zeolites may be used in amounts of, forexample, 0.1 to 20 parts by weight, expediently 0.1 to 10 parts byweight and in particular 0.1 to 5 parts by weight, based on 100 parts byweight of halogen-containing polymer.

Katoites

Compounds suitable for the inventive stabilizer combinations from thegroup of the katoites can be described by the general formulaCa₃Al₂(OH)₁₂.mH₂O,where

-   -   m=0-10.

The compounds mentioned may, if appropriate, have been surface-modified.They have a very particular crystal lattice, (known as hydrogarnetstructure), which distinguishes them from other calcium aluminum hydroxycompounds.

This crystal lattice, together with lattice separations, is described inthe article by C. Cohen-Addad and P. Ducros in Acta Cryst. (1967), 23,pages 220 to 225. By way of example, these materials may be prepared bya method based on German patent specification DE 2 424 763.

Hydrocalumites

Compounds suitable for the inventive stabilizer combinations and derivedfrom the group of the hydrocalumites are described by the generalformula:Ca_(x)Al (OH)_(2x+3).mH₂O,where

-   -   x=1 to 4 and    -   m=from 0 to 8.

Preferred compounds are those where, in the above general formula,x=2 or 3.Calcium Aluminum Hydroxy(Hydrogen)Phosphites

Suitable compounds from the group of the basic CHAPs, calcium aluminumhydroxyhydrogenphosphites, have the general formulaCa_(x)Al₂(OH)_(2(x + 2))HPO ⋅ m  H₂O, where x = from  2  to  8  andm = from  0  to  12, orCa_(x)Al₂(OH)_(2(x + 3 − y))(HPO₃)_(y) ⋅ m  H₂O, where${x = {{from}\quad 2\quad{to}\quad 12}},{\frac{{2x} + 5}{2} > y > {0\quad{and}}}$m = from  0  to  12,with the exception y=1, if x=from 2 to 8.

Other examples of the hydrocalumites which via variation of the metalcation M and of the acid anions A or B of the general formula belowM²⁺ _((2+x))Al³⁺ _((1+y)) (OH)_((6+z))A^(j−) _(a)[B_(r)]^(nl)*mH2Oand are described in detail in patent specification WO 02/098964, pages18-20. In one preferred embodiment, M is calcium, which may be presentin a mixture with magnesium or zinc or magnesium and zinc. For thepurposes of the preferred embodiment, the composition is selected to befree from the heavy metal zinc. If a surface treatment is desired, theproduct may be modified accordingly using the methods and reagents knownto the person skilled in the art.Lithium Layer-Lattice Compounds

Lithium aluminum layer-lattice compounds have the general formula ALi_(a)MII_((b-2a))Al_((2+a))OH_((4+2b))An^(−2/n).mH₂Owhere

-   -   MII is Mg, Ca or Zn and    -   An⁻ is a selected anion of valency n or a mixture of anions    -   and the indices are in the range    -   0<a<(b-2)/2,    -   1<b<6 and    -   m=from 0 to 30    -   with the proviso that b-2a>2 or    -   the general formula B        [Al₂(Li_((1-x)).MII_(x)) (OH)₆]n (An⁻)_(1+x)mH₂O        where    -   -MII, A, m and n are as defined above and x complies with the        condition 0.01≦x<1.

The preparation of the layer-lattice compounds mentioned ischaracterized by reacting lithium hydroxide, lithium oxide and/or itscompounds capable of conversion to hydroxide, metal(II) hydroxides,metal(II) oxides and/or their compounds derived from the metalsmentioned and capable of conversion to hydroxides, and aluminumhydroxides and/or their compounds capable of conversion to hydroxides,and also acids and/or their salts or mixtures thereof with one anotherin an aqueous medium, at a pH of from 8 to 10 and at temperatures offrom 20 to 250° C., and isolating the resultant solid product of thereaction. The reaction time is preferably 0.5 to 40 hours, in particularfrom 3 to 15 hours.

The product directly produced from the reaction described above can beisolated from the aqueous reaction medium by known processes, preferablyvia filtration. The product isolated from the reaction is also worked upin a manner known per se, for example via washing of the filter cakewith water and drying of the washed residue at temperatures of, forexample, from 60 to 150° C., preferably at from 90 to 120° C. For thereaction with aluminum it is possible to use either fine-particle,activated metal(III) hydroxide in combination with sodium hydroxide orto use an NaAlO2. Lithium, or one of the metal(II) compounds mentioned,may be used in the form of fine-particle lithium oxide or fine-particlelithium hydroxide, or a mixture thereof, or in the form of fine-particlemetal(II) oxide or fine-particle metal(II) hydroxide or a mixturethereof. The corresponding acid anions may be used at variousconcentrations, e.g. directly in the form of acid or else in the form ofsalt.

The reaction temperatures are preferably from about 20 to 250° C., moreparticularly from about 60 to 180° C. Catalysts or accelerators are notrequired. The water of crystallization of the substances may be removedentirely or partially by heating.

In their use as stabilizers, the dried layer-lattice compounds do notevolve water or any other gas at the usual processing temperatures offrom 160 to 220° C. for PVC, and therefore no blistering defects occurin the moldings.

The anion An in the above general formula can be sulfate, sulfite,sulfide, thiosulfate, peroxide, peroxosulfate, peroxodisulfate,hydrogenphosphate, hydrogenphosphite, carbonate, halides, nitrate,nitrite, hydrogensulfate, hydrogencarbonate, hydrogensulfite,hydrogensulfide, dihydrogenphosphate, dihydrogenphosphite,monocarboxylic anions, such as acetate and benzoate, amide, azide,hydroxide, hydroxylamine, hydroazide, acetylacetonate, phenolate,pseudohalides, halites, halates, perhalates, periodate, permanganate,dianions of dicarboxylic acids, e.g. phthalate, oxalate, maleate orfumarate, bisphenolates, phosphate, pyrophosphate, phosphite,pyrophosphite, trianions of tricarboxylic acids, e.g. citrate,trisphenolates, and many others, or else a mixture thereof. Among these,preference is given to hydroxide, carbonate, phosphite and maleate.

To improve the dispersibility of the substances in halogen-containingthermoplastic polymer compositions, these may be surface-treated with ahigher fatty acid, e.g. stearic acid, with an anionic surfactant, with asilane coupling agent, with a titanate coupling agent, or with aglycerol ester of a fatty acid.

The calcium aluminum hydroxides, calcium aluminumhydroxohydrogenphosphites, aluminum hydroxides, calcium aluminum hydroxo(hydrogen) carbonates and lithium layer-lattice compounds des-cribedabo-ve may be nbt only crystalline but also semicrystalline and/oramorphous.

Fillers

Fillers such as calcium carbonate, dolomite, wollastonite, magnesiumoxide, magnesium hydroxide, silicates, china clay, talc, glass fibers,glass beads, wood flour, mica, metal oxides or metal hydroxides, carbonblack, graphite, rock flour, heavy spar, glass fibers, talc, kaolin andchalk are used. Preference is given to chalk (HANDBOOK OF PVCFORMULATING E. J. Wickson, John Wiley & Sons, Inc., 1993, pp. 393-449)and reinforcing agents (TASCHENBUCH der Kunststoff-additive [PlasticsAdditives Handbook], R. Gächter & H. Müller, Carl Hanser, 1990, pp.549-615).

The fillers may be used in amounts of preferably at least one part byweight, for example 5 to 200 parts by weight, expediently 10 to 150parts by weight and in particular from 15 to 100 parts by weight, basedon 100 parts by weight of PVC.

Metal Soaps

Metal soaps are primarily metal carboxylates, preferably of relativelylong-chain carboxylic acids. Well-known examples of these are stearatesand laurates, and also oleates and salts of relatively short-chainaliphatic or aromatic alkanecarboxylic acids, such as acetic acid,propionic acid, butyric acid, valeric acid, hexanoic acid, sorbic acid;oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,fumaric acid, citric acid, benzoic acid, salicylic acid, phthalic acids,hemimellitic acid, trimellitic acid, pyromellitic acid.

Metals which should be mentioned are: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al,La, Ce and rare earth metals. Use is frequently made of so-calledsynergistic mixtures, such as barium zinc stabilizers, magnesium/-zincstabilizers, calcium/zinc stabilizers or calcium/ magnesium/zincstabilizers. The metal soaps may be used either alone or in mixtures. Anoverview of common metal soaps is found in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Ed., Vol. A16 (1985), pp. 361 et seq. Besidesthe compounds mentioned, use may also be made of organoaluminumcompounds, and of compounds analogous to the abovementioned compounds,in particular aluminum tristearate, aluminum distearate, and aluminummonostearate, and also aluminum acetate and basic derivatives derivedtherefrom.

U.S. Pat. No. 4,060,512 and U.S. Pat. No. 3,243,394 give furtherexplanations concerning the aluminum compounds which can be used andthose which are preferred.

Besides the abovementioned compounds, use may also be made of organicrare earth compounds, in particular compounds analogous to theabovementioned compounds. The term rare earth compound meansparticularly compounds of the elements cerium, praseodymium, neodymium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, lutetium, lanthanum and yttrium, particularpreference being given to mixtures with cerium. Other preferred rareearth compounds are found in EP-A-0 108 023. Examples of the amount ofthe metal soaps or their mixtures which may be used are from 0.001 to 10parts by weight, advantageously from 0.01 to 8 parts by weight,particularly preferably from 0.05 to 5 parts by weight, based on 100parts by weight of PVC.

Compounds of Alkali Metals and of Alkaline Earth Metals

For the purposes of the present invention, these are mainly thecarboxylates of the acids described above, but also corresponding oxidesor, respectively, hydroxides or carbonates. Mixtures of these withorganic acids are also possible. Examples are LiOH, NaOH, KOH, CaO,Ca(OH)₂, MgO, Mg(OH)₂, Sr(OH)₂, Al(OH)₃, CaCO₃ and MgCO₃ (and also basiccarbonates, such as magnesia alba and huntite), and also fatty-acidsalts of Na and of K. In the case of alkaline earth metal carboxylatesand Zn carboxylates it is also possible to use adducts of these with MOor M(OH)₂ (M═Ca, Mg, Sr or Zn), so-called “overbased” compounds. Inaddition to the stabilizers according to the invention it is preferableto use alkali metal carboxylates, alkaline earth metal carboxylatesand/or aluminum carboxylates.

Lubricants

Examples of possible lubricants are: montan wax, fatty acid esters,(ox.) polyethylene waxes, polypropylene waxes, (ox.) paraffin waxes,amide waxes, chloroparaffins, glycerol esters and alkaline earth metalsoaps, and fatty ketones, and also the lubricants, or combinations ofthe lubricants, listed in EP 0 259 783, based on complex esters. Otherlubricants which may be used are mentioned in “Plastics AdditivesHandbook”, Carl Hanser Verlag, 5th edition, 2001, pages 511-552.

Plasticizers

Examples of organic plasticizers are those from the following groups:

A) Phthalates: such as preferably di-2-ethylhexyl, diisononyl anddiisodecyl phthalate, also known by the common abbreviations DOP(dioctyl phthalate, di-2-ethylhexylphthalate), DINP (diisononylphthalate), DIDP (diisodecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, in particular esters ofadipic, azelaic, and sebacic acid: preferably di -2-ethylhexyl adipateand diisooctyl adipate.

C) Trimellitic esters, such as tri-2-ethylhexyl trimellitate,triisodecyl trimellitate (mixture), triisotridecyl trimellitate,triisooctyl trimellitate (mixture), and also tri-C₆-C₈-alkyl,tri-C₆-C₁₀-alkyl, tri-C₇-C₉-alkyl and tri-C₉-C₁₁-alkyl trimellitate.Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyltrimellitate), TIDTM (triisodecyl trimellitate) and TITDTM(triisotridecyl trimellitate). D) Epoxy plasticizers: by way of examplehere, mention may be made of epoxidized unsaturated fatty acids, e.g.epoxidized soybean oil, epoxidized linseed oil, epoxidized sunfloweroil, epoxidized rapeseed oil, epoxidized tallow oil, epoxidized oliveoil. Other epoxidized fatty acid esters which may be mentioned are thevariants based on the monoesters of fatty acids and on monohydricalcohols, disclosed in WO 02/060884 A1. Other variants of epoxidizedfatty acid esters are produced via transesterification of, for example,triacetin, described in DE-A-30 04 660. Among these are the epoxidizedglyceride acetates, obtainable by transesterifying epoxidized fatty acidesters with triacetin. The molar ratio here can be selected so that, ifdesired, the appropriate diglyceride monoacetates are quantitativelypredominant. Detailed examples and processes are disclosed in patentspecification WO 02/060884 A1. The preparation of other derivatives,such as the monoglyceride diacetates, is also disclosed in US-A2-895966. All of the mixtures as described actually mostly comprise complexmixtures derived from the transesterification reactions.

E) Polymeric plasticizers: the commonest starting materials forpreparing polyester plasticizers are: dicarboxylic acids, such asadipic, phthalic, azelaic or sebacic acid; diols, such as1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol,neopentyl glycol and diethylene glycol.

F) Phosphoric esters: a definition of these esters is given in theabovementioned “Taschenbuch der Kunststoffadditive ” [“Plasics AdditivesHandbook”], Chapter 5.9.5, pp. 408-412. Examples of these phosphoricesters are tributyl phosphate, tri-2-ethylbutyl phosphate,tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyldiphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate,tricresyl phosphate and trixylenyl phosphate. Preference is given totris(2-ethylhexyl) phosphate and Reofos® 50 and 95 (CibaSpezialitätenchemie).

G) Chlorinated hydrocarbons (paraffins)

H) Hydrocarbons

I) Monoesters, e.g. butyl oleate, phenoxyethyl oleate,tetrahydrofurfuryl oleate and alkylsulfonates.

J) Glycol esters, e.g. diglycol benzoates.

K) Representatives of citric acid plasticizers Among these are thecitric esters of the general formula B, derived from2-hydroxy-1,2,3-propanetricarboxylic acid as described in WO 02/094927R1-O—C— (COOR) (CH₂—COOR)₂   Bwhere

each R is a straight-chain or branched alkyl radical having from 4 to 18carbon atoms and R1═H, or R1═R2CO. If R1 is not H, R2 is astraight-chain or branched alkyl radical having from 1 to 10 carbonatoms. Preferred alcohol components R used in the citric ester areC6-C14 alkanols, which may be branched or unbranched, and the alkanolradicals here may be identical or different.

Compounds which may be listed as non-restricting examples are triethylcitrate (Citrofol A I), tributyl citrate (Citrofol B I), triethylacetylcitrate (Citrofol A II), tributyl acetylcitrate (Citrofol B II),tri-n-hexyl acetylcitrate, tri-n-hexyl n-butyryl-citrate,tri-n-(hexyl/octyl/decyl) acetylcitrate and tri-n-(octyl/decyl)acetylcitrate.

L-) Perhydrophthalic, perhydraisophthalic and perhydro-terepihthalicesters, and also perhydrogenated glycol benzoate and perhydrogenateddiglycol benzoate esters. Preference is given to perhydrogenateddiisononyl phthalate (®Hexamoll DINCH—BASF) as described in DE19.756.913, DE 19.927.977, DE 19.927.978 and DE 19.927.979.

A definition of these plasticizers and examples of the same are given in“Kunststoffadditive” [“Plastics Additives”], R. Gächter/H. Müller, CarlHanser Verlag, 3rd Ed., 1989, Chapter 5.9.6, pp. 412-415, and in “PVCTechnology”, W. V. Titow, 4th Ed., Elsevier Publ., 1984, pp. 165-170. Itis also possible to use mixtures of different plasticizers.

Examples of the amount which may be used of the plasticizers are 5 to 20parts by weight, expediently 10 to 20 parts by weight, based on 100parts by weight of PVC. Rigid or semirigid PVC preferably comprises upto 10%, particularly preferably up to 5%, of plasticizer, or noplasticizer.

Pigments

Suitable substances are known to the person skilled in the art. Examplesof inorganic pigments are TiO₂, pigments based on zirconium oxide,BaSO₄, zinc oxide (zinc white) and lithopones (zinc sulfide/bariumsulfate), carbon black, carbon black-titanium dioxide mixtures, ironoxide pigments, Sb₂O₃, (Ti,Ba,Sb) O₂, Cr₂O₃, spinels, such as cobaltblue and cobalt green, Cd(S,Se), ultramarine blue. Examples of organicpigments are azo pigments, phthalocyanine pigments, quinacridonepigments, perylene pigments, diketo-pyrrolopyrrole pigments andanthraquinone pigments. TiO₂ in micronized form is also preferred. Adefinition and further descriptions are found in the “Handbook of PVCFormulating”, E. J. Wickson, John Wiley & Sons, New York, 1-993.

Phosphites

Organic phosphites are known costabilizers for chlorine-containingpolymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl,tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl,trisnonyl-phenol, tris-2,4-tert-butylphenyl or tricyclohexyl phosphite.

Other suitable phosphites are various mixtures of aryl dialkyl or alkyldiaryl phosphites, e.g. phenyl dioctyl, phenyl didecyl, phenyldidodecyl, phenyl ditridecyl, phenyl ditetradecyl, phenyl dipentadecyl,octyl diphenyl, decyl diphenyl, undecyl diphenyl, dodecyl diphenyl,tridecyl diphenyl, tetradecyl diphenyl, pentadecyl diphenyl, oleyldiphenyl, stearyl diphenyl and dodecyl bis-2,4-di-tert-butylphenylphosphite.

It is also advantageous to use phosphites of various di- or polyols:examples are tetraphenyl dipropylene glycol diphosphite, polydipropyleneglycol phenyl phosphite, tetramethylolcyclohexanol decyl diphosphite,tetramethylolcyclohexanol butoxyethoxyethyl diphosphite,tetramethylolcyclohexanol nonylphenyl diphosphite, bisnonylphenylditrimethylolpropane diphosphite, bis-2-butoxyethyl ditrimethylolpropanediphosphite, trishydroxyethyl isocyanurate hexadecyl triphosphite,didecyl pentaerythrityl diphosphite, distearyl pentaerythrityldiphosphite, bis-2,4-di-tert-butylphenyl pentaerythrityl diphosphite,and also mixtures of these phosphites and aryl/alkyl phosphite mixturesof empirical composition(H₁₉C₉C₆H₄)O_(1.5)P(OC_(12, 13)H_(25, 27))_(1.5) or[C₈H₁₇—C₆H₄—O—]₂P[i-C₈H₁₇O], (H₁₉C₉C₆H₄)O_(1.5)P(OC_(9, 11)H_(19, 23))_(1.5).

An example of the amount which may be used of the organic phosphites isfrom 0.01 to 10 parts by weight, advantageously from O.0:5 to 5 parts byweight, and in particular from 0.1 to 3 parts by weight, based on 100parts by weight of PVC.

Epoxidized Fatty Acid Esters and other Epoxy Compounds

The inventive stabilizer combination may also preferably comprise atleast one epoxidized fatty acid ester. Esters of fatty acids fromnatural sources (fatty acid glycerides) may especially be used here,examples being soy oil or rapeseed oil. However, it is also possible touse synthetic products, such as epoxidized butyl oleate. It is alsopossible to use epoxidized polybutadiene and polyisoprene, ifappropriate also in partially hydroxylated form, or glycidyl acrylateand glycidyl methacrylate in the form of homo- or copolymer. These epoxycompounds may also have been applied to an alumino salt compound; inthis connection see also DE-A-4 031 818.

Antioxidants

Alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol,alkylthiomethylphenols, e.g. 2,4-dioctylthio-methyl-6-tert-butylphenol,alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol,hydroxylated thiodiphenyl ethers, e.g.2,2′-thiobis(6-tert-butyl-4-methylphenol), alkylidenebisphenols, e.g.2,2′-methylenebis(6-tert-butyl-4-methylphenol), benzyl compounds, e.g.3,5,3′,5′-tetra-tert-butyl-4,4′-di-hydroxydibenzyl ether,hydroxybenzylated malonates, e.g. dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxy-benzyl)malonate,hydroxybenzylaromatics, e.g.1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-tri-methylbenzene,triazine compounds, e.g.2,4-bisoctyl-mercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,phosphonates and phosphonites, e.g. dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acyl-aminophenols, e.g.4-hydroxylauranilide, esters of beta-(3,5-di-tert-butyl-4-hydroxypLenyl)propionic acid, ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid, ofbeta-(3,5-dicyclohexyl-4-hydroxy-phenyl)propionic acid, esters of3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydricalcohols, amides of beta-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionicacid, e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,vitamin E (tocopherol), and derivatives.

An example of the amount which may be used of the antioxidants is from0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts byweight, and in particular from 0.1 to 5 parts by weight, based on 100parts by weight of PVC.

UV Absorbers and Light Stabilizers

Examples of these are: 2-(2′-hydroxyphenyl)benzo-triazoles, such as2-(2′-hydroxy-5′-methylphenyl)-benzotriazole, 2-hydroxybenzophenones,esters of unsubstituted or substituted benzoic acids, such as4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickelcompounds, oxalamides, such as 4,4′-dioctyloxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,2-(2-hydroxyphenyl)-1,3,5-triazines, such as2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,sterically hindered amines, such asbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate.

Blowing Agents

Examples of blowing agents are organic azo compounds and organic hydrazocompounds, tetrazoles, oxazines, isatoic anhydride, and also soda andsodium bicarbonate. Preference is given to azodicarbonamide and sodiumbicarbonate and also mixtures of these.

Definitions and examples of impact modifiers and processing aids,gelling agents, antistats, biocides, metal deactivators, opticalbrighteners, flame retardants, antifogging agents, and compatibilizers,are described in “Kunststoffadditive” [“Plastics Additives”], R.Gächter/H. Müller, Carl Hanser Verlag, 3rd edn., 1989, “PlasticsAdditives Handbook” H. Zweifel, Carl Hanser Verlag, 5th edn., 2001 andin “Handbook of Polyvinyl Chloride Formulating” E. J. Wilson, J. Wiley &Sons, 1993, and also in “Plastics Additives” G. Pritchard, Chapman &Hall, London, 1st edition, 1998.

Impact modifiers are also described in detail in “Impact Modifiers forPVC”, J. T. Lutz/D. L. Dunkelberger, John Wiley & Sons, 1992.

The invention further provides compositions which comprise achlorine-containing polymer and comprise an inventive stabilizermixture.

The amount used of the compounds of the general formulae (I) in thesecompositions, in order to achieve stabilization in thechlorine-containing polymer, is advantageously from 0.01 to 10 parts byweight, preferably from 0.05 to 5 parts by weight, in particular from0.1 to 2 parts by weight, based on 100 parts by weight of PVC.

The amount used of the compounds of the general formulae (II) in thesecompositions, in order to achieve stabilization in thechlorine-containing polymer, is advantageously from 0.01 to 10 parts byweight, preferably from 0.05 to 5 parts by weight, in particular from0.1 to 2 parts by weight, based on 100 parts by weight of PVC.

The amount used of the compounds of the general formulae (III) in thesecompositions, in order to achieve stabilization in the chlorinecontaining polymer, is advantageously from 0.01 to 10 parts by weight,preferably from 0.05 to 5 parts by weight, in particular from 0.1 to 2parts by weight, based on 100 parts by weight of PVC.

An example of the amount which may be used of the perchlorate salt isfrom 0.001 to 5 parts by weight, advantageously from 0.01 to 3 parts byweight, particularly preferably from 0.01 to 2 parts by weight, based on100 parts by weight of PVC.

Examples of the chlorine-containing polymers to be stabilized are:polymers of vinyl chloride, of vinylidene chloride, vinyl resins whosestructure contains vinyl chloride units, such as copolymers of vinylchloride and vinyl esters of aliphatic acids, in particular vinylacetate, copolymers of vinyl chloride with esters of acrylic ormethacrylic acid and with acrylonitrile, copolymers of vinyl chloridewith diene compounds and with unsaturated dicarboxylic acids oranhydrides of these, such as copolymers of vinyl chloride with diethylmaleate, diethyl fumarate or maleic anhydride, postchlorinated polymersand copolymers of vinyl chloride, copolymers of vinyl chloride andvinylidene chloride with unsaturated aldehydes, ketones and others, suchas acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether,vinyl isobutyl ether and the like; polymers of vinylidene chloride andcopolymers of the same with vinyl chloride and with other polymerizablecompounds; polymers of vinyl chloroacetate and of dichlorodivinyl ether;chlorinated polymers of vinyl acetate, chlorinated polymeric esters ofacrylic acid and of alpha-substituted acrylic acid; polymers ofchlorinated styrenes, such as dichlorostyrene; chlorinated rubbers;chlorinated polymers of ethylene; polymers and postchlorinated polymersof chlorobutadiene and copolymers of these with vinyl chloride,chlorinated natural or synthetic rubbers, and also mixtures of thepolymers mentioned with themselves or with other polymerizablecompounds. For the purposes of this invention, PVC includes copolymerswith polymerizable compounds, such as acrylonitrile, vinyl acetate orABS, where these may be suspension polymers, bulk polymers or elseemulsion polymers. Preference is given to a PVC homopolymer, also incombination with polyacrylates.

Other possible polymers are graft polymers of PVC with EVA, ABS or MBS.Other preferred substrates are mixtures of the abovementioned homo- andcopolymers, in particular vinyl chloride homopolymers, with otherthermoplastic or/and elastomeric polymers, in particular blends withABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM or withpolylactones, in particular from the group consisting of ABS, NBR, NAR,SAN and EVA. The abbreviations used for the copolymers are familiar tothe skilled worker and have the following meanings: ABS:acrylonitrile-butadiene-styrene; SAN: styrene-acrylonitrile; NBR:acrylonitrile-butadiene; NAR: acrylonitrile-acrylate; EVA:ethylene-vinyl acetate. Other possible polymers are in particularstyrene-acrylonitrile copolymers based on acrylate (ASA). A preferredcomponent in this context is a polymer composition which comprises, ascomponents (i) and (ii), a mixture of 25-75% by weight of PVC and 75-25%by weight of the copolymers mentioned. Components of particularimportance are compositions made from (i) 100 parts by weight of PVC and(ii) 0-300 parts by weight of ABS and/or SAN-modified ABS and 0-80 partsby weight of the copolymers NBR, NAR and/or EVA, but in particular EVA.For the purposes of the present invention it is also possible tostabilize in particular recycled materials of chlorine-containingpolymers, specifically the polymers described in more detail above,which have been degraded by processing, use or storage. Recycledmaterial from PVC is particularly preferred.

The compounds which may be used concomitantly according to theinvention, and also the chlorine-containing polymers, are well known tothe skilled worker and are described in detail in “Kunststoffadditive”[“Plastics Additives”], R. Gächter/H. Müller, Carl Hanser Verlag, 3rdedn., 1989; in DE 197 41 778 and in EP-A 99 105 418.0 of 03.17.1999,which are incorporated herein by way of reference.

The inventive stabilizer system for chlorine-containing polymercompositions is represented by non-plasticized or plasticizer-free, orsubstantially plasticizer-free. compositions.

The inventive compositions are particularly suitable in the form ofunplasticized formulations for hollow articles (bottles), packagingfoils (thermoforming foils), blown foils, crash-pad foils (automobiles),pipes, foams, heavy profiles (window frames), thin-wall profiles,construction profiles, external cladding, fittings, office foils, andapparatus casings (computers, household devices). Preferred othercompositions in the form of plasticized formulations are suitable forwire sheathing, cable insulation, decorative foils, roof sheeting,foams, agricultural sheeting, hoses, sealing profiles, office foils, andsheeting for air-supported structures.

Examples of use of the inventive compositions in the form of plastisolsare synthetic leather, flooring, textile coatings, wallcoverings, metalcoatings (coil coatings), and underbody protection for motor vehicles.Examples of sintered-PVC uses of the inventive compositions are slush,metal coatings and coil coatings, and Luvitherm foils in the EPVCsector.

The stabilizers may advantageously be incorporated by the followingmethods: in the form of an emulsion or disperesoin (an example of apossibile form being that of a paste-like mixture, and an advantage ofthe inventive combination in that supply form being the stability of thepaste); in the form of a dry mixture during the mixing of addedcomponents or polymer mixtures; via direct addition to the processingapparatus (e.g. calender, mixer, kneader, extruder, or the like), or inthe form of a solution or melt or flakes or granules/pellets indust-free form in the form of a one-pack system.

The inventive stabilized PVC likewise provided by the invention can beprepared in a manner known per se, and to this end the inventivestabilizer mixture and, if appropriate, other additives are mixed withthe PVC, using apparatus known per se, such as the above-mentionedprocessing apparatus. The stabilizers here can be added individually orin a mixture, or else in the form of what are known as masterbatches.

The PVC stabilized by the present invention may be converted to thedesired form by known methods. Examples of these processes are milling,calendering, extrusion, injection molding, or spinning, or elseextrusion blow molding. The stabilized PVC can also be processed to givefoams.

By way of example, a PVC stabilized according to the invention isparticularly suitable for hollow articles (bottles), packaging foils(thermoforming foils), blown foils, pipes, foams, heavy profiles (windowframes), thin-wall profiles, construction profiles, external cladding,fittings, office foils, and apparatus casings (computers, householddevices).

The inventive PVC is particularly suitable for semi-rigid andplasticized formulations, in particular in the form of plasticizedformulations for wire sheathing, or cable insulation, which isparticularly preferred. In the form of semirigid formulations, theinventive PVC is particularly suitable for decorative foils, foams,agricultural sheeting, hoses, sealing profiles, and office foils.

Examples of use of the inventive PVC in the form of plastisol aresynthetic leather, flooring, textile coatings, wall, coverings, metalcoatings coil coatings and underbody protection for motor vehicles.

Examples of sintered-PVC uses of the PVC stabilized according to theinvention are slush coatings and coil coatings for plastisolformulations, for semirigid formulations, and for plasticizedformulations. For further details in this connection, see“Kunststoffhandbuch PVC” [Plastics handbook PVC], vol. 2/2, W. Becker/H.Braun, 2nd edn., 1985, Carl Hanser Verlag, pages 1236-1277.

The examples below illustrate the invention but do not restrict thesame. As in the rest of the description, data relating to parts andpercentages are based on weight.

EXAMPLES

The composition of test formulations as in the tables is given below.The data are in parts by weight, based on 100 parts of PVC resin.

A laboratory extruder was used to extrude strips in accordance with theformulations, starting from the respective dry mixtures. To produce thestrips, the PVC powder mixtures and the additives mentioned wereprepared by the conventional hot/cold mixing technique and homogenizedand plastified in a twin-screw extruder.

The extrusion parameters are ads follows: Weber CE-3, conical twinscrew: screw rotation rate 13 rpm, temperature control in individualzones: barrel section in zone 1: 170° C., zone 2 at 165° C., zone 3 at170° C., and zone 4 at 180° C. The die temperature was adjusted to 190°C. Die geometry: 50×2 mm.

Initial color was determined as yellowness index (YI) to ASTM D1925-70.The results are given in the tables below. Low YI values mean goodstabilization.

Long-term stability was further determined via determination of thermalstability to DIN VDE 0472. Here, the test piece was heated to 200° C. ina glass tube in an oil bath, the bottom of which had been sealed byfusion (AR glass from Peco-Laborbedarf GmbH, Darmstadt), and the time atwhich visible red coloration of the universal pH indicator paper wasobserved (corresponding to pH of 3) was determined.

The stability of the PVC was further determined via thedehydrochlorination test (DHC test), carried out by a method based onDIN 53381, sheet 3. Here, the time required for the dehydrochlorinationcurve to rise to a conductivity of 200 μS/cm was measured at 180° C.

Example 1

A 1 A 2 A 3 A 4 A 5 A 6 A 7 PVC (Shin Etsu 6704) 100 100 100 100 100 100100 Compound 1 — — — — — — 0.1 Zeolite A 1.0 1.0 1.0 1.0 1.0 1.0 1.0Calcium stearate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Marklube 367 0.6 0.6 0.60.6 0.6 0.6 0.6 Licowax PE 520 0.6 0.6 0.6 0.6 0.6 0.6 0.6 AC 629 A 0.10.1 0.1 0.1 0.1 0.1 0.1 1,3-Dimethyl-4- — 0.1 0.2 — — 0.1 0.1aminouracil TEA — — — 0.1 0.2 0.1 0.1 Test results Color measurementYellowness Index red- 31 26 73 73 27 23 extruded strip/ violet initialcolorPVC Shin Etsu 6704, K value 67 (ex Shin Etsu)Compound 1 = mixture composed of 9% NaClO₄, 45% CaCO₃, 40% CaSiO₃, 6%H₂OMarklube 367 = paraffin wax (ex Crompton)Licowax PE 520 = polyethylene wax (ex Clariant)AC 629 A = oxidized polyethylene wax (ex Honeywell)TEA = triethanolamine in the form of commercially available product1,3-dimethyl-4-aminouracil in the form of commercially available product

From the table it can be seen that the inventive composition A6 hassurprising stabilizer action when compared with the comparativemixtures. This clearly meets an objective of this invention, improvementof initial color. For assessment of processing properties, the initialcolor of the test specimen is especially important for providingsufficient processing stability. Even small differences in the YI valuehere are relevant. The particular effect of a combination of compoundsof the structure (I) with compounds of the structure (II) is seen to besignificant here. The compound of the formula (I), used alone, does nothave a satisfactory effect on the initial color of the PVC, as shown bythe comparative examples A 4 and A 5. Synergistic action is onlyreleased in combination with a compound of formula (II), as shown inexample A6. It can also be seen that the stabilization of the polymervia use of alkanolamines in combination with uracils can be stillfurther raised via addition of perchlorates, as stated in inventiveexample A7.

Example 2

A 4 A 5 B 1 B 2 B 3 PVC (Shin Etsu 6704) 100 100 100 100 100 Compound 1— — — — — Zeolite A 1.0 1.0 1.0 1.0 1.0 Calcium stearate 0.4 0.4 0.4 0.40.4 Marklube 367 0.6 0.6 0.6 0.6 0.6 Licowax PE 520 0.6 0.6 0.6 0.6 0.6AC 629 A 0.1 0.1 0.1 0.1 0.1 N,N′-Dimethyl-N- — — 0.1 0.2 0.1cyanoacetylurea TEA 0.1 0.2 — — 0.1 Test results Color measurementYellowness Index 73 73 36 30 28 extruded strip/ initial colorPVC Shin Etsu 6704, K value 67 (ex Shin Etsu)Compound 1 = mixture composed of 9% NaClO₄, 45% CaCO₃, 40% CaSiO₃, 6%H₂OMarklube 367 = paraffin wax (ex Crompton)Licowax PE 520 = polyethylene wax (ex Clariant)AC 629 A = oxidized polyethylene wax (ex Honeywell)TEA = triethanolamine in the form of commercially available product

From the table it can be seen that the inventive composition B3 hasimproved stabilizer action when compared with the comparative mixtures.This clearly meets an objective of this invention, improvement ofinitial color. For assessment of processing properties, the range ofinitial color of the test specimen is especially important. Theparticular effect of a combination of compounds of the structure (I)with compounds of the structure (III) is seen to be significant here.

Example 3/1

The following formulations were roll-milled at 1800C for 5 minutes onmixing rolls. The milled sheet formed was used to produce a pressedsheet at 180° C. in a preheated multi-daylight sheet press. Pressedsheet thickness: 1 mm, press time: 1 minute. Yellowness index wasdetermined to ASTM D1925-70. Low YI values mean good stabilization and,respectively, initial color. High percentages mean good transparency. C1 C 2 C 3 C 4 C 5 C 6 C 7 Evipol SH 5730 100 100 100 100 100 100 100Paraloid_(BTA III/N2) 5 5 5 5 5 5 5 Paraloid K 120N 0.5 0.5 0.5 0.5 0.50.5 0.5 Paraloid K 175 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E wax 0.3 0.3 0.3 0.30.3 0.3 0.3 Loxiol G 16 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Epox. soybean oil3.0 3.0 3.0 3.0 3.0 3.0 3.0 NaP/H₂O 0.6 0.6 0.6 0.6 0.6 0.6 0.6 TEA 0.20.4 — — 0.2 0.2 0.2 1,3-Dioctyl-4-amino- — — 0.1 0.3 0.1 0.2 0.2 uracilMark CH 300 0.5 Color measurement on 1 mm pressed sheets YellownessIndex YI 43.8 36.1 83.1 54.4 24.4 18.4 14.8 Transparency 90.5 91.1 78.089.9 92.3 93.1 92.9Evipol SH 5730 PVC, K value 57 (ex EVC)Paraloid K 175/K 120N = acrylate processing aid (ex Rohm & Haas)Paraloid BTA III/N2 = methacrylate-butadiene-styrene modifier (ex Rohm &Haas)E wax = ester wax/montan wax (ex Clariant)Loxiol G 16 = fatty acid partial ester (ex Henkel)NaP/H₂O = 30% strength sodium perchlorate solution in waterMark CH 300 = mixed aryl/alkyl phosphite (ex Crompton)TEA = triethanolamine in the form of commercially available product

From the table it can be seen that the inventive composition C 5provides an improvement in stabilizer action when compared with thecomparative mixtures. It can also be seen that stabilization of thepolymer via use of alkanolamines in combination with uracils can bestill further raised via addition of phosphites, as stated in inventiveexample C 7.

Example 3/2

The formulations were roll-milled at 180° C. for 5 minutes on mixingrolls. The milled sheet formed was used to produce a pressed sheet at180° C. in a preheated multi-daylight sheet press. Pressed sheetthickness: 1 mm, press time: 1 minute. Yellowness index was determinedto ASTM D1925-70. Low YI values mean good stabilization and,respectively, initial color. High percentages mean good transparency. C1 C 2 C 8 C 9 C 10 C 11 C 12 Evipol SH 5730 PVC 100 100 100 100 100 100100 Paraloid BTA III/N2 5 5 5 5 5 5 5 Paraloid K 120N 0.5 0.5 0.5 0.50.5 0.5 0.5 Paraloid K 175 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E wax 0.3 0.3 0.30.3 0.3 0.3 0.3 Loxiol G 16 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Epox. soybeanoil 3.0 3.0 3.0 3.0 3.0 3.0 3.0 NaP/H₂O 0.6 0.6 0.6 0.6 0.6 0.6 0.6 TEA0.2 0.4 — — 0.2 0.2 0.2 1,3-Dimethyl-4- — — 0.1 0.3 0.1 0.2 0.2aminouracil Phosphite Mark 0.5 CH 300 Color measurement on 1 mm pressedsheets Yellowness Index YI 43.8 36.1 55.7 24.1 16.3 14.2 11.6Transparency 90.5 91.1 88.8 91.1 92.8 92.5 92.6Evipol SH 5730 PVC, K value 57 (ex EVC)Paraloid K175/K 120N = acrylate processing aid (ex Rohm & Haas)Paraloid BTA III/N2 = methacrylate-butadiene-styrene modifier (ex Rohm &Haas)E wax = ester wax/montan wax (ex Clariant)Loxiol G 16 = fatty acid partial ester of glycerol (ex Henkel)NaP/H₂O = 30% strength sodium perchlorate solution in waterPhosphite Mark CH 300 = mixed aryl/alkyl phosphite (ex Crompton)TEA = triethanolamine in the form of commercially available product

From the table it can be seen that the inventive compositions C 10 and C11 provide an improvement in stabilizer action when compared with thecomparative mixtures. It can also be seen that stabilization of thepolymer via use of alkanolamines in combination with uracils can bestill further raised via addition of phosphites, as stated in inventiveexample C 12.

Example 4

The following formulations were roll-milled at 180° C. for 5 minutes onmixing rolls. The milled sheet formed was used to produce a pressedsheet at 180° C. in a preheated multi-daylight sheet press. Pressedsheet thickness: 1 mm, press time: 1 minute. Yellowness index wasdetermined to ASTM D1925-70. Low YI values mean good stabilization and,respectively, initial color. High percentages mean good transparency.The Congo Red value was determined at 200° C. to DIN 473/811/3/2. Highminute values mean good thermal stability of the test specimen. The timetaken to reach conductivity of 200 μS/cm was measured. The higher thevalue from this dehydrochlorination test (DHC), the better thestabilization. D 1 D 2 D 3 D 4 D 5 D 6 D 7 D 8 PVC (Evipol SH 7020) 100100 100 100 100 100 100 100 DEHP 20 20 20 20 20 20 20 20 Epox. soybeanoil 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 NaP/BDG 0.2 0.2 0.2 0.2 0.2 0.2 0.20.2 AC 629 A 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 TEA 0.2 0.4 — — 0.2 — — —Diethanolsoyamine — — — — — 0.2 0.4 0.2 1,3-Dibutyl-4-aminouracil — —0.2 0.3 0.1 — — 0.1 Color measurement on 1 mm pressed sheets YellownessIndex YI 17.4 14.7 15.8 12.2 9.7 15.7 13.9 9.1 Transparency 96.7 95.997.3 97.4 97.3 97.6 97.6 98.1 Congo Red 17 28 10 10 21 10 22 17 DHC[200□S/cm] 117 152 88 93 128 89 129 115Evipol 7020 PVC, K value 70 (ex EVC)DEHP = di-2-ethylhexyl phthalate in the form of commercially availableproductNaP/BDG = 30% strengh sodium perchlorate solution in butyl diglycolTEA = triethanolamine in the form of commercially available productDiethanolsoyamine = bis(2-hydroethyl)soyamine in the form ofcommercially available product1,3-Dibutyl-4-aminourcilAC 629 A = oxidized polyethylene wax (ex Honeywell)

From the table it can be seen that the inventive compositions D5 and D8have improved stabilizer action when compared with the comparativemixtures.

Example 5

The formulations were roll-milled at 180° C. for 5 minutes on mixingrolls. The milled sheet formed was used to produce a pressed sheet at180° C. in a preheated multi-daylight sheet press. Pressed sheetthickness: 1 mm, press time: 1 minute. Yellowness index was determinedto ASTM D1925-70. Low YI values mean good stabilization and,respectively, initial color. High percentages mean good transparency. E1 E 2 E 3 E 4 E 5 E 6 E 7 E 8 E 9 E 10 E 11 Evipol SH 100 100 100 100100 100 100 100 100 100 100 7020 PVC DEHP 47 47 47 47 47 47 47 47 47 4747 Epox. 3 3 3 3 3 3 3 3 3 3 3 soybean oil Loxiol G 71 S 0.3 0.3 0.3 0.30.3 0.3 0.3 0.3 0.3 0.3 0.3 Calcium 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 stearate NaP/BDG — — — — — — — — 0.5 0.5 0.5 1,3-Dioctyl- — 0.20.2 0.2 0.2 0.2 0.2 0.2 4-aminouracil TEA — 0.2 0.2 0.2Diethanolsoyamine 0.2 0.2 0.2 TIPA 0.2 0.2 0.2 Color measurement on 1 mmpressed sheets Yellowness 66.3 56.1 24.3 13.9 87.2 18.2 72.5 17.0 10.29.6 9.6 Index YI b value 21.9 23.4 14.2 10.7 23.9 10.7 30.4 10.1 5.7 5.65.8 Transparency 74.7 85.2 97.5 97.8 66.4 97.8 84.6 97.9 96.5 96.8 97.6Evipol SH 7020 PVC, K value 70 (ex EVC)DEHP = di-2-ethylhexyl phthalate in the form of commercially availableproductNaP/BDG = 30% strength sodium perchlorate solution in butyl diglycolLoxiol G 71 S = multicomponent ester lubricant (ex Henkel)TEA = triethanolamine in the form of commercially available productDiethanolsoyamine = ES-2 in the form of commercially availble productTIPA = triisopropanolamine in the form of commercially availble product

From the table it can be seen that the inventive compositions E4, E6,and E8 provide an improvement in stabilizer action when compared withthe comparative mixtures. It can also be seen that stabilization of thepolymer can be still further raised via addition of perchlorate, asstated in inventive examples E9, E10, and E11.

1. A stabilizer mixture for stabilizing chlorine-containing polymers,comprising at least a) one alkanolamine of the following formula (I),and b) one uracil of the following formula (II), wherein, for thealkanolamine of the formula (I)

x=1,2or3; y=1,2,3,4,5or6; n=from 1 to 10; R¹ and R₂=independently of oneanother H, C₁-C₂₂-alkyl, —[—(CHR³ _(a))_(y)—CHR³ _(b)—O—]_(n)—H,—[—(CHR³ _(a))_(y)—CHR³ _(b)—O—]_(n)—CO—R⁴, C₂-C₂₀-alkenyl, C₂-C₁₈-acyl,C₄-C₈-cyclo-alkyl, where this may have OH substitution in theβ-position, C₆-C₁₀-aryl, C₇-C₁₀-alkaryl or C₇-C₁₀-aralkyl, or, if x=1,R¹ and R² may also, together with the N, form a closed ring having from4 to 10 members, composed of carbon atoms and, where appropriate, of upto 2 heteroatoms, or if x=2, R¹ may also be C₂-C₁₈-alkylene which, atboth β-carbon atoms, may have OH substitution and/or have interruptionby one or more O atoms and/or by one or more NR² groups, or bedihydroxy-substituted tetrahydrodicyclopentadienylene,dihydroxy-substituted ethylcyclohexanylene, dihydroxy-substituted4,4′-(bisphenol A dipropyl ether)ylene, isophoronylene,dimethylcyclohexanylene, dicyclohexylmethanylene or3,3′-dimethyldicyclohexylmethanylene, and if x=3, R¹ may also betrihydroxy-substituted (tri-N-propyl isocyanurate)triyl; R³ _(a) and R³_(b)=independently of one another C₁-C₂₂-alkyl, C₂-C₆-alkenyl,C₆-C₁₀-aryl, H or CH₂—X—R⁵, where X═O, S, —O—CO— or —CO—O—;R⁴═C₁-C₁₈-alkyl/alkenyl or phenyl; and R⁵═H, C₁-C₂₂-alkyl,C₂-C₂₂-alkenyl or C₆-C₁₀-aryl; and for the uracil of the formula (II)

R₁ and R₂, independently of one another, are C₁-C₂₄-alkyl, which mayhave interruption by —CO₂— and/or by 1 or more oxygen atoms, and/or mayhave substitution by one or more OH groups, or are C₃-C₂₄-alkenyl,branched or unbranched, or are C₅-C₈-cycloalkyl, unsubstituted orsubstituted with from 1 to 3 C₁-C₄-alkyl, C₁-C₄-alkoxy, orC₅-C₈-cycloalkyl groups, or with hydroxy groups, or with C, atoms, orare C₇-C₉-phenylalkyl, unsubstituted or substituted on the phenyl ringwith from 1 to 3 C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₅-C₈-cycloalkyl groups,or with hydroxy groups, or with Cl atoms, and R1 or R2 may also behydrogen, and Y is S or O.
 2. A stabilizer mixture for stabilizingchlorine-containing polymers of claim 1, comprising at least a) onereaction product of a mono- or polyfunctional epoxide and of ammonia orof a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine ofthe formula (I), and b) one uracil of the formula (II).
 3. A stabilizermixture for stabilizing chlorine-containing polymers of claim 1,comprising at least a) one alkanolamine of the formula (I), and b) onecyanoacetylurea of the following formula (III) (III)

wherein Y is oxygen or sulfur, and R₂ is C₁-C₂₄-alkyl, which may haveinterruption by —CO₂— and/or by oxygen atoms, and/or may havesubstitution by from I to 3 OH groups, or is C₃-C₂₄-alkenyl,C₇-C₁₀-phenylalkyl, C₅-C₈-cycloalkyl, C₇-C₁₀-alkylphenyl, phenyl ornaphthyl, Use and in each case the aromatic radical may havesubstitution by —OH, C₁-C₁₂-alkyl and/or OC₁-C₄-alkyl, and R₁ is asdefined for R₂, or R₁ is hydrogen.
 4. A stabilizer mixture forstabilizing chlorine-containing polymers of claim 3, comprising at leasta) one reaction product of a mono- or polyfunctional epoxide and ofammonia or of a mono- or polyfunctional dialkyl(aryl)- ormonoalkyl(aryl)amine of the formula (I), and b) a cyanoacetylurea of theformula (III).
 5. The stabilizer mixture as claimed in claim 2, whereinthe polyfunctional epoxide is dicyclopentadiene diepoxide,vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, ortrisglycidyl isocyanurate, and the dialkylamine is diethanolamine ordiisopropanolamine, and the monoalkylamine is monoethanolamine ormonoisopropanolamine.
 6. The stabilizer mixture as claimed claim 1,wherein, in the compound with the general formula (I), R³ _(a) and R³_(b), independently of one another, are H or CH₃ and y=1.
 7. Thestabilizer mixture as claimed in claim 1, wherein, in the compound withthe general formula (I), R¹═R²═CH₂—CHR³ _(b)—OH.
 8. The stabilizermixture as claimed in claim 1, wherein the compounds of the generalformula (I) are tris(2-hydroxy-1-propyl)amine,tris(2-hydroxyethyl)amine, bis(2-hydroxyethyl)-2-hydroxy-1-propyl)amine,or alkyl/alkenyl-bis(2-hydroxyethyl)amine,alkyl/alkenyl(2-hydroxy-1-propyl)amine,N-(2-hydroxyhexadecyl)diethanolamine,N-(2-hydroxy-3-octyloxypropyl)diethanolamine,N-(2-hydroxy-3-decyloxypropyl)diethanol-amine, or a mixture thereof. 9.The stabilizer mixture for stabilizing chlorine-containing polymers, asclaimed in claim 1, also comprising at least one perchlorate salt. 10.The stabilizer mixture as claimed in claim 1, wherein the perchloratesalt is a compound of the formula M(ClO₄)_(n), wherein M is Li, Na, K,Mg, Ca, Sr, Ba, Zn, Al, La, Ce, or a hydrotalcite layer-lattice cation,or an organic onium cation; n is 1, 2 or 3, as appropriate for thevalency of M, or if a hydrotalcite layer-lattice cation is present0<n≦1.
 11. The stabilizer mixture as claimed in claim 1, wherein, in theperchlorate salt, M═Na or K, and n=1.
 12. The stabilizer mixture asclaimed in claim 1, also comprising an anhydrous hydrotalcite or azeolite.
 13. The stabilizer mixture as claimed in claim 1, which also,if appropriate, comprises metal soaps, and/or, if appropriate, comprisesanother substance from the group of the polyols and disaccharidealcohols, salts of the hydroxycarboxylic acids, glycidyl compounds,hydrotalcites, aluminosilicates of alkali metals or of alkaline earthmetals, hydroxides/oxides of alkali metals or of alkaline earth metals,or the corresponding (hydrogen)carbonates or carboxylates, andfillers/pigments, plasticizers, antioxidants, light stabilizers, opticalbrighteners, lubricants and epoxidized fatty acid esters.
 14. Thestabilizer mixture as claimed in claim 1, where a phosphite is alsopresent, and/or possible reaction products of phosphite with thecomponent of formula (I) or with the perchlorate salt are present. 15.The stabilizer mixture as claimed in claim 1, where the additionalphosphite is distearyl pentaerythrityl diphosphite, triphenyl phosphite,trisnonylphenyl phosphite, phenyl didecyl phosphite, poly(dipropyleneglycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite,tetraisodecyl dipropylene glycol diphosphite, trisdipropylene glycolphosphite, decyl diphenyl phosphite, trioctyl phosphite, trilaurylphosphite or nonylphenyl_(1.5) C₁₂/C₁₃-alkyl_(1.5) phosphite.
 16. Acomposition, comprising a chlorine-containing polymer and the stabilizermixture as claimed in claim
 1. 17. The composition as claimed in claim1, wherein it comprises, based on 100 parts by weight ofchlorine-containing polymer, from 0.01 to 10 parts by weight of thecompound of the general formula (I) and from 0.01 to 10 parts by weightof the compound of the general formula (II).
 18. The composition asclaimed in claim 1, wherein it comprises, based on 100 parts by weightof chlorine-containing polymer, from 0.01 to 10 parts by weight of thecompound of the general formula (I) and from 0.01 to 10 parts by weightof the compound of the general formula (III).
 19. The composition asclaimed in claim 17, wherein it also comprises, based on 100 parts byweight of chlorine-containing polymer, from 0.001 to 5 parts by weightof the perchlorate salt.
 20. The composition as claimed in claim 19,wherein it also comprises, based on 100 parts by weight ofchlorine-containing polymer, from 0.05 to 5 parts by weight of aphosphite.
 21. A process for stabilizing chlorine-containing polymersvia addition of the stabilizer mixture as claimed in claim 1,chlorine-containing polymer.
 22. The process for stabilizingchlorine-containing polymers as claimed in claim 21, wherein thechlorine-containing polymer is plasticized PVC.
 23. The process forstabilizing chlorine-containing polymers as claimed in claim 21, whereinthe plasticized PVC serves for production of floorcoverings, motorvehicle components, plasticized foils, hoses, injection moldings, orwire sheathing.
 24. The process for stabilizing chlorine-containingpolymers as claimed in claim 21, wherein the chlorine-containing polymeris unplasticized PVC.
 25. The process for stabilizingchlorine-containing polymers as claimed in claim 21, wherein thechlorine-containing polymer serves for production of foils, or of PVCpipes, or of profiles.
 26. A consumer item, comprising PVC, which hasbeen stabilized via the stabilizer mixture as claimed in claim 1.